WO2017038349A1 - Retort-packaging polypropylene-based sealant film and laminate using same - Google Patents
Retort-packaging polypropylene-based sealant film and laminate using same Download PDFInfo
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- WO2017038349A1 WO2017038349A1 PCT/JP2016/072637 JP2016072637W WO2017038349A1 WO 2017038349 A1 WO2017038349 A1 WO 2017038349A1 JP 2016072637 W JP2016072637 W JP 2016072637W WO 2017038349 A1 WO2017038349 A1 WO 2017038349A1
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- film
- resistance
- low
- propylene
- retort
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Definitions
- the present invention relates to a polypropylene-based sealant film for retort packaging and a laminate using the same, and in particular, it has excellent low-temperature impact resistance and distorted skin resistance, and excellent sealing strength, blocking resistance and bending whitening resistance.
- the present invention relates to a polypropylene sealant film for retort packaging that can be widely used for high retort applications as a large retort packaging bag, and a laminate thereof.
- an unstretched film (hereinafter sometimes referred to as CPP) mainly composed of a propylene / ethylene block copolymer has been used. I came.
- PET polyethylene terephthalate
- ON nylon stretched film
- Al foil aluminum foil
- the CPP that constitutes the innermost surface is required to have properties such as low-temperature impact resistance, heat-sealing properties, crushed skin resistance, and blocking resistance.
- properties such as low-temperature impact resistance, heat-sealing properties, crushed skin resistance, and blocking resistance.
- the size of pouches for business use has increased, and the required level of further low temperature impact resistance has increased.
- the quality requirement level of the pouch appearance is also increasing, and it is desired to suppress the occurrence of fine uneven appearance, that is, so-called crushed skin, which occurs on the surface of the laminate after retort sterilization as much as possible.
- Patent Document 1 in order to achieve both low-temperature impact resistance and blocking resistance, a polymer part (A component) mainly composed of propylene and an ethylene / propylene copolymer part (B component) are prepared by a gas phase method.
- a component mainly composed of propylene and an ethylene / propylene copolymer part (B component)
- B component ethylene / propylene copolymer part
- the intrinsic viscosity ratio of the A component and the B component is regulated to be a certain value or less and the low molecular weight ratio of the xylene soluble part is suppressed
- the low temperature impact resistance is fundamental.
- the dependence of bag drop strength on bag making conditions was unsatisfactory.
- the same applicant as in Patent Document 1 has also proposed in Patent Document 2 that the component A is a propylene / ethylene copolymer having an ethylene content of 0.5 to 1.5% by weight. .
- Patent Document 3 proposes that a small amount of high-density polyethylene be blended with the propylene / ethylene block copolymer whose amount of xylene solubles is specified. In some cases, low temperature impact resistance deteriorated.
- Patent Document 4 in order to obtain a film having good blocking resistance and heat sealability, the amount of components of the ethylene / propylene copolymer portion is increased, and the intrinsic viscosity is increased. Although it has also been proposed to specify the intrinsic viscosity, when such a film is used, the low temperature impact resistance and blocking resistance are improved, but the ethylene / propylene copolymer portion, which is a rubber component, has a relatively large island shape. Because of this, there was a problem that the skin resistance when the oily food was encapsulated was not good. *
- Patent Document 5 has a disclosure in which an ethylene copolymer elastomer is blended with a specific propylene / ⁇ -olefin block copolymer in order to provide such a film having a good skin.
- a propylene / ethylene block copolymer that defines the relationship between intrinsic viscosity of para-xylene soluble part and insoluble part and ethylene / ⁇ -olefin copolymer having a specific intrinsic viscosity for the purpose of improving the resistance to bending whitening.
- specific propylene / ethylene blocks can be used to provide a sealant film with excellent content visibility, specifically transparency in terms of haze, visual see-through properties, and excellent bending whitening.
- Proposed polypropylene film composed of components Patent Document 7
- the amount of rubber component in the main propylene / ethylene block copolymer to satisfy low-temperature impact resistance, heat sealability, bending whitening resistance, crushed skin resistance, blocking resistance, etc. at a high level In addition to adjusting the molecular weight, a proposal (Patent Document 8) comprising an ethylene / ⁇ -olefin copolymer and a polyethylene polymer has been made, and a sealant film and a laminate having a very good balance can be provided.
- Patent Document 8 comprising an ethylene / ⁇ -olefin copolymer and a polyethylene polymer has been made, and a sealant film and a laminate having a very good balance can be provided.
- a higher level of low-temperature impact resistance may be required, which may not be satisfied.
- the amount of the rubber component in the main propylene / ethylene block copolymer and the molecular weight thereof are adjusted, and the ethylene / ⁇ -olefin copolymer, the polyethylene polymer and the styrene block copolymer, or the crystallinity.
- Patent Document 9 a proposal composed of an olefin block
- the quality required for the sealant for retort packaging has been increasingly demanded in recent years in order to cope with the increase in the size of commercial pouches.
- the low temperature impact resistance is still insufficient, and none has been found that satisfies all of the properties such as the generation of crushed skin, the blocking resistance, and the heat seal strength at a high level in a well-balanced manner.
- the present invention is for retort packaging that can be widely used for high retort packaging as a large retort packaging bag that is excellent in low-temperature impact resistance, and also excellent in the generation of crushed skin, seal strength, blocking resistance, and bending whitening resistance.
- a polypropylene sealant film and a laminate using the same are provided.
- the polypropylene sealant film for retort packaging according to the present invention comprises a resin composition containing at least 70 to 85% by weight of a propylene / ethylene block copolymer (a) and 15 to 30% by weight of a low density polyethylene polymer (b).
- the propylene / ethylene copolymer (a) has a ratio of xylene insoluble part at 20 ° C.
- a polypropylene sealant film for retort packaging having a density of b) of 0.900 to 0.930 g / cm 3 and a melt flow rate of 1 to 10 g / 10 min.
- the present invention is the above-described polypropylene sealant film for retort packaging, wherein the low density polyethylene polymer (b) is a linear low density polyethylene.
- the present invention is a laminate in which the sealant film is laminated on one side of a base material layer in which a single layer or two or more layers are laminated.
- the polypropylene-based sealant film for retort packaging of the present invention has a very high level of low-temperature impact resistance and crushed skin resistance, and is also excellent in seal strength, blocking resistance, and bending whitening resistance. It can be used as a sealant film suitable for retort packaging.
- the laminate of the present invention is very excellent in bag drop strength, can preferably cope with the increase in size of pouches for business use, etc., and even when oily foods are packaged, it is difficult to produce crushed skin, etc.
- a retort packaging bag having good sealing strength and the like can be provided.
- the polypropylene sealant film for retort packaging according to the present invention is a film comprising a resin composition containing 70 to 85% by weight of a propylene / ethylene block copolymer (a) and 15 to 30% by weight of a low density polyethylene polymer (b). It is.
- the proportion of the 20 ° C. xylene insoluble part is 75 to 85% by weight with respect to (a) 100% by weight, and the intrinsic viscosity of the insoluble part (hereinafter referred to as [ ⁇ ] May be referred to as H. ) is 1.7 to 2.0 dl / g, and the intrinsic viscosity of the soluble part (hereinafter also referred to as [ ⁇ ] EP ) is 3.0 to 3.4 dl / g. g is required.
- xylene insoluble part and the soluble part are the above-mentioned propylene / ethylene block copolymer pellets completely dissolved in boiling xylene, then cooled to 20 ° C. and allowed to stand for 4 hours or more.
- the precipitate is referred to as a 20 ° C. xylene insoluble portion
- the portion obtained by drying the solution portion (filtrate) at 70 ° C. under reduced pressure is referred to as the soluble portion.
- the xylene-insoluble part corresponds to a sea component composed of polypropylene in the propylene / ethylene block copolymer
- the xylene-soluble part corresponds to an island component composed of an ethylene / propylene copolymer rubber component.
- the ratio of the insoluble part to the soluble part needs to be in the range of 75 to 85% by weight. If the insoluble part is smaller than 75% by weight, the ratio of the soluble part is large. Thus, blocking resistance, heat resistance, rigidity, and heat seal strength are reduced. If the insoluble part is larger than 85% by weight, the low temperature impact resistance due to the contribution of the soluble part is insufficient.
- the intrinsic viscosity of the xylene-insoluble portion ([ ⁇ ] H) is 1.7 ⁇ 2.0 dl / g, when the limiting viscosity ([ ⁇ ] H) is less than 1.7 dl / g, polypropylene sea component
- the molecular weight is small, the low-temperature impact resistance and the bending whitening resistance are insufficient.
- the molecular weight is larger than 2.0 dl / g, the molecular weight of polypropylene becomes too large and cast molding becomes difficult.
- the intrinsic viscosity ([ ⁇ ] EP ) of the xylene-soluble part is 3.0 to 3.4 dl / g.
- the low density polyethylene polymer (b) to the propylene / ethylene block copolymer (a)
- the seal strength is significantly reduced unless the intrinsic viscosity ([ ⁇ ] EP ) is 3.0 dl / g or more.
- it exceeds 3.4 dl / g a yuzu skin phenomenon will generate
- the xylene-soluble part preferably has an ethylene content in the range of 20 to 50% by weight. If the content is less than 20% by weight, the low-temperature impact resistance at low temperatures is lowered. Conversely, if the content is more than 50% by weight, the blocking resistance tends to be insufficient.
- the low-density polyethylene polymer (b) described above is added to the propylene / ethylene block copolymer (a), and the low-temperature impact resistance is improved by increasing the components having a glass transition point lower than that of polypropylene. Moreover, the generation
- Such a low density polyethylene polymer (b) needs to contain 15 to 30% by weight as a composition ratio in the polypropylene sealant film for retort packaging of the present invention.
- the polyethylene polymer is less than 15% by weight, the effect of improving low temperature impact resistance, resistance to generation of crushed skin, and resistance to bending whitening is insufficient, or conversely, when it exceeds 30% by weight, Blocking resistance may be reduced, and processability and bag opening may be deteriorated.
- the melt flow rate of the propylene / ethylene block copolymer (a) includes a cast moldability viewpoint, a low temperature impact resistance decrease, a gel,
- MFR propylene / ethylene block copolymer
- the range of 0.5 to 5 g / 10 minutes is preferable from the viewpoint of fear of the occurrence of fish eyes, and more preferably the range is 1 to 3.5 g / 10 minutes. If the MFR is less than 0.5, the melt viscosity is too high, and it is difficult to stably extrude from the die during film formation. If the MFR exceeds 5, the low temperature impact resistance may deteriorate.
- the propylene / ethylene block copolymer (a) is polymerized.
- Add molecular weight modifiers such as hydrogen gas and metal compounds in each step add additives when melt-kneading and pelletizing polymer obtained in powder form, melt polymer obtained in powder Examples thereof include a method of adjusting kneading conditions when kneading and pelletizing.
- the method of polymerizing propylene, ethylene, etc. which are raw materials using a catalyst is mentioned.
- a Ziegler-Natta type, metallocene catalyst or the like can be used as the catalyst, and for example, those described in JP-A-07-216017 can be suitably used.
- a polymer portion mainly composed of propylene in the first step substantially in the absence of an inert solvent is used. It is preferable to use a method of polymerizing and then polymerizing an ethylene / propylene copolymer in the gas phase in the second step.
- the polymer portion mainly composed of propylene is preferably a propylene homopolymer having a melting point of 160 ° C. or higher from the viewpoint of heat resistance, rigidity and the like. It may be a copolymer with a small amount of ⁇ -olefin such as ethylene and 1-butene.
- the density of the low density polyethylene polymer (b) used in the present invention is preferably in the range of 0.900 to 0.930 g / cm 3 .
- the polyethylene polymer refers to ethylene alone or ethylene and an ⁇ -olefin having 3 or more carbon atoms such as propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene and the like.
- a polymer which is produced by a generally known method can be used.
- high-pressure low-density polyethylene and linear low-density polyethylene can be used.
- linear low-density polyethylene has higher impact strength and higher sealing strength than high-pressure low-density polyethylene.
- Low density polyethylene is preferred.
- the melt flow rate (MFR, unit g / 10 minutes) at 190 ° C. of the low density polyethylene copolymer (b) is 1 to 10 g / 10 minutes from the viewpoint of low temperature impact resistance and heat sealability. It is a range. Preferably, a range of 1 to 5 g / 10 minutes is exemplified. If the MFR is less than 1, flow unevenness due to melt fracture tends to occur. Conversely, if the MFR exceeds 10, the low temperature impact resistance and the seal strength may be deteriorated.
- the polypropylene sealant film for retort packaging according to the present invention is obtained by mixing the above two components (a) and (b) by an ordinary method and molding the resulting mixture into a film by an ordinary method. It is done.
- the melt film forming method include an inflation method, a die method, a calendar method, and the like, and the die method can be particularly preferably employed.
- the resulting kneaded material is filtered through a filter, and a flat die (for example, T die) Or it can manufacture by extruding into a film form from a cyclic
- the temperature of the molten polymer extruded from the melt extruder can usually be 200 to 300 ° C., but 220 to 270 ° C. is preferable in order to prevent degradation of the polymer and obtain a film of good quality.
- the extruded film When extruding from a T-die, the extruded film is brought into contact with a cooling roll set at a constant temperature of 20 to 65 ° C., cooled and solidified, and then wound.
- a cooling roll set at a constant temperature of 20 to 65 ° C.
- bubbles are formed by a method generally called an inflation method, cooled and solidified, and then wound up.
- the polypropylene sealant film for retort packaging of the present invention can be stretched after cooling and solidification, but is preferably an unstretched film that is not substantially stretched.
- a non-stretched film that is not substantially stretched is preferable because it is excellent in tear strength and does not need to excessively increase the heat seal temperature during heat sealing, that is, it can be heat-sealed at a relatively low temperature.
- the unstretched film refers to an extruded cast film. However, in the actual film forming process, the film may be slightly oriented in the longitudinal direction or the width direction of the film.
- the birefringence of the stretched film refers to 0.005 or less.
- the thickness of the polypropylene sealant film for retort packaging of the present invention is 20 to 300 ⁇ m, more preferably 40 to 100 ⁇ m.
- the polypropylene sealant film for retort packaging of the present invention can be used alone as a packaging film, but can also be preferably used as a sealant film for retort food packaging bags containing a general Al foil.
- the polypropylene sealant film for retort packaging of the present invention is an antioxidant, a heat stabilizer, a neutralizing agent, an antistatic agent, a hydrochloric acid absorbent, an antiblocking agent, a lubricant, and a nucleating agent as long as the object of the present invention is not impaired. Agents and the like. These additives may be used alone or in combination of two or more.
- antioxidants include hindered phenols such as 2,6-di-t-butylphenol (BHT), n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate (“Irganox” 1076, “Sumilizer” BP-76), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (“Irganox”) "1010," Sumilizer "BP-101), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (“ Irganox "3114, Mark AO-20), etc.
- BHT 2,6-di-t-butylphenol
- Irganox n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl
- phosphite (phosphorus) antioxidants tris (2,4-di-t-butylphenyl) phosphite (“Irgafos” 168, Mark 2112), tetrakis (2,4-di-t-butyl) Phenyl) -4-4′-biphenylene-diphosphonite (“Sandstab” P-EPQ), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (“Ultranox” 626, Mark PEP-24G), And distearyl pentaerythritol diphosphite (Mark PEP-8).
- the amount of the antioxidant added may be appropriately set in the range of 0.05 to 0.3% by weight, although it depends on the kind of the antioxidant used.
- hydrotalcite compounds are preferable for reducing smoke generation during film formation.
- a resin component other than the propylene / ethylene block copolymer (a) and the low-density polyethylene polymer (b) is added to the polypropylene sealant film for retort packaging of the present invention as long as the object of the present invention is not impaired. It is possible. However, the addition of a styrene-based elastomer can improve low-temperature impact resistance and scratch resistance, but it is preferable not to add it because it reduces blocking resistance and heat seal strength.
- the polypropylene sealant film for retort packaging according to the present invention is usually subjected to industrial corona discharge treatment, corona discharge treatment under nitrogen or carbon dioxide atmosphere, plasma treatment, ozone treatment, as required. It is also possible to perform surface treatment such as.
- the present invention also relates to a laminate using the above-described polypropylene sealant film for retort packaging.
- the laminate of the present invention comprises a polypropylene-based sealant film for retort packaging of the present invention (here, the film of the present invention) on one side of a substrate layer in which a single layer or two or more transparent films and an aluminum foil are laminated. And is laminated).
- a polypropylene-based sealant film for retort packaging of this invention was laminated
- Typical examples of these are PET film / AL foil / present film, PET film / ON / AL foil / present film, PET film / AL foil / ON / present film, ON / present film.
- a normal dry laminating method in which an adhesive is used to bond to the constituent films of the laminate can be suitably employed.
- the laminate of the present invention and the substrate layer can be directly applied.
- a method of extruding and laminating a polypropylene resin can also be adopted.
- These laminates are used by forming the film of the present invention into a flat bag, a standing pouch or the like, using the film of the present invention as a sealing layer on the inner surface of the bag.
- the laminated structure of these laminates has the required characteristics of packaging bags, such as barrier performance to meet the quality retention period of the food to be packed, size / low temperature impact resistance that can handle the weight of the contents, and visibility of the contents It is appropriately selected depending on the above.
- Low temperature impact resistance Polypropylene sealant film of the present invention subjected to corona discharge treatment with a PET film having a thickness of 12 ⁇ m, a stretched nylon film having a thickness of 15 ⁇ m, an AL foil having a thickness of 9 ⁇ m and a corona discharge treatment (herein referred to as the present invention film) are laminated by a normal dry laminating method using a urethane-based adhesive to produce a laminate having the following configuration.
- Laminate structure PET film / adhesive / ON / adhesive / AL foil / adhesive / inventive film Two of these laminates were used as CA-450 manufactured by Fuji Impulse Co., Ltd. with the inventive film as the inner surface of the bag.
- a standing pouch having a bag size of 150 mm ⁇ 285 mm was prepared with a heating time of 1.4 seconds (sealing temperature: about 220 ° C.) and a cooling time of 3.0 seconds.
- the bag is filled with 1000 cm 3 of 0.1% saline solution, and then retorted at 135 ° C. for 30 minutes.
- each bag is dropped from a height of 55 cm onto a flat floor (n number: 20), and the number of times until the bag is broken is recorded.
- n number 20
- the number of times until the bag is broken is recorded. In this evaluation method, the number of n is 20, and if the average number of times until the bag breaks is 35 times or more, it can be used well for large retort for business use.
- rank 1 The rating was evaluated as rank 1 for those that did not occur at all, rank 2 for those that occurred slightly, rank 3 for those that slightly occurred, rank 4 for those that occurred clearly, and rank 5 that occurred severely.
- ranks 1 and 2 were evaluated as good for the generation of scum skin.
- Blocking resistance A sample of the film of the present invention subjected to a corona discharge treatment having a width of 30 mm and a length of 100 mm was prepared, and a seal layer which is a non-corona treated surface was overlapped in a range of 30 mm ⁇ 40 mm to obtain 500 g / After applying a load of 12 cm 2 and heat-treating in an oven at 80 ° C. for 24 hours, leaving it in an atmosphere of 23 ° C. and 65% humidity for 30 minutes or more, using Tensilon manufactured by Orientec Co., Ltd., 300 mm / min. The shear peel force was measured at the tensile speed. In this measurement method, if the shear peeling force was 25 N / 12 cm 2 or less, it was regarded as a practical range.
- Example 1 The following were used for the propylene / ethylene block copolymer (a) and the low density polyethylene polymer (b).
- Propylene / ethylene block copolymer (a) The content of the 20 ° C. xylene insoluble part is 80% by weight, its intrinsic viscosity ([ ⁇ ] H ) is 1.90 dl / g, the content of the 20 ° C. xylene soluble part is 20% by weight, its intrinsic viscosity ([ ⁇ ] EP ) is 3.20 dl / g, MFR at 230 ° C. is 2.3 g / 10 min, and propylene / ethylene block copolymer pellets containing “Sumilizer” GP 300 ppm and “Sumilizer” GS 750 ppm as antioxidants are used. did.
- L-LDPE Linear low density polyethylene
- MFR 2.0 g / 10 min
- L-LDPE copolymerization component of 1-hexene
- Example 2 A 70 ⁇ m thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) used in Example 1 was changed to (a) 70 wt% and (b) 30 wt%. It was.
- the resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- Example 3 A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) used in Example 1 was changed to (a) 85 wt% and (b) 15 wt%. It was.
- the obtained film is slightly inferior to the skin-resistant skin, but at a level that does not cause any problems. It has excellent low-temperature impact resistance, sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- Example 4 As the low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Prime Polymer Co., Ltd.) having a density of 0.903 g / cm 3 and a copolymerization component of MFR 3.8 g / 10 min of 1-hexene. SP0540) was used. A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- Example 5 A low density polyethylene polymer (b) having a density of 0.920 g / cm 3 and a MFR of 7.0 g / 10 min (hereinafter sometimes referred to as LDPE) (manufactured by Sumitomo Chemical Co., Ltd.) L705) was used. A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- LDPE low density polyethylene polymer having a density of 0.920 g / cm 3 and a MFR of 7.0 g / 10 min
- Example 6 A propylene / ethylene block copolymer having a 20% xylene insoluble part ratio of 83% ([ ⁇ ] H : 1.92 dl / g, [ ⁇ ] EP : 3.25 dl / g) was prepared and implemented. A 70 ⁇ m thick film was obtained in the same manner as in Example 1. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- Example 7 A propylene / ethylene block copolymer having a 20% xylene insoluble part ratio of 77% ([ ⁇ ] H : 1.86 dl / g, [ ⁇ ] EP : 3.10 dl / g) was prepared and carried out. A 70 ⁇ m thick film was obtained in the same manner as in Example 1. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
- Example 2 is 2.0 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Irgaphos”
- a film having a thickness of 70 ⁇ m was obtained in the same manner as in Example 1 except that the pellets were changed to propylene / ethylene block copolymer pellets containing 168 in 250 ppm.
- the resulting film had good resistance to low-temperature impacts, although it had good resistance to scratching skin, blocking resistance, heat sealability, and resistance to bending whitening.
- Example 2 is 2.5 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Sumilizer” A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that the propylene / ethylene block copolymer pellets containing GP 300 ppm and “Sumilizer” GS 750 ppm were used.
- the obtained film was poor in low-temperature impact resistance, blocking resistance, and heat-sealability, although it had good resistance to scratching skin and bending whitening resistance.
- Example 2 is 2.2 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Sumilizer” A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that the propylene / ethylene block copolymer pellets containing GP 300 ppm and “Sumilizer” GS 750 ppm were used.
- the obtained film had poor scratch resistance and heat-sealability, although it had good skin resistance, low-temperature impact resistance and bending whitening resistance.
- Example 5 A propylene / ethylene block copolymer having a 20% xylene insoluble portion ratio of 82% ([ ⁇ ] H : 1.65 dl / g, [ ⁇ ] EP : 3.11 dl / g) was prepared and carried out. A 70 ⁇ m thick film was obtained in the same manner as in Example 1. The obtained film was excellent in resistance to generation of scratches and was excellent in seal strength and blocking resistance, but was insufficient in low-temperature impact resistance and anti-bending whitening resistance.
- Example 6 A 70 ⁇ m thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) in Example 1 was changed to (a) 65 wt% and (b) 35 wt%.
- the obtained film had poor scratch resistance and heat-sealability, although it had good skin resistance, low-temperature impact resistance and bending whitening resistance.
- Example 7 A 70 ⁇ m thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) in Example 1 was changed to (a) 90 wt% and (b) 10 wt%. Although the obtained film had good blocking resistance and heat sealability, it was inferior in resistance to low-temperature impact, resistance to crushed skin, and resistance to bending whitening.
- the low density polyethylene polymer (b) has a density of 0.960 g / cm 3 and a MFR of 16.0 g / 10 min.
- High density polyethylene hereinafter sometimes referred to as HDPE (KEIYO manufactured by Keiyo Polyethylene Co., Ltd.) Polyethylene G1900) was used.
- a 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. Although the obtained film had good crushed skin resistance, it was inferior in low-temperature impact resistance and heat sealability.
- Example 9 As the low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) having a density of 0.935 g / cm 3 and an MFR of 3.0 g / 10 min as a copolymer component of 1-butene. GA401) was used. A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and scratch resistance, and has excellent sealing strength, blocking resistance, and bending whitening resistance. It was insufficient for large retort applications.
- a low density polyethylene polymer (b) As a low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Prime Polymer Co., Ltd.) having a density of 0.914 g / cm 3 and a copolymerization component of 11.0 g / 10 min of MFR of 1-hexene. 15100C) was used. A 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The obtained film was particularly excellent in low temperature impact resistance and resistance to generation of crushed skin, and was excellent in blocking resistance and bending whitening resistance, but had low sealing strength and impact resistance. However, the performance was insufficient for large retort applications for business use.
- VLDPE very low density polyethylene
- MFR 3.0 g / 10 min (Affinity manufactured by Dow Chemical Co., Ltd.) KC8852G)
- a 70 ⁇ m-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The obtained film was excellent in low-temperature impact resistance and anti-bending whitening resistance, but was insufficient in the generation of crushed skin, seal strength, and blocking resistance.
- the polypropylene-based sealant film for retort packaging of the present invention is particularly excellent in low-temperature impact resistance, resistance to generation of crushed skin, combined with blocking resistance, heat sealability, bending whitening resistance, etc., and used for large retort packaging for business use. Moreover, it can be used as a suitable sealant film.
- the laminate of the present invention has the above-described polypropylene sealant film for retort packaging laminated as a heat seal layer, by using this laminate, it is particularly excellent in resistance to low-temperature impacts and resistance to skin damage.
- a retort packaging bag can be provided.
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Abstract
Description
(2)有機アルミニウム化合物、
(3)電子供与性化合物(ジアルキルジメトキシシラン等が好ましく用いられる)よりなる触媒系が挙げられる。 Specifically, (1) in the presence of an organosilicon compound having an Si—O bond and an ester compound, the general formula Ti (OR) a X 4-a (wherein R is a hydrocarbon having 1 to 20 carbon atoms) A titanium compound represented by the following formula: X represents a halogen atom, a represents a number of 0 <a ≦ 4, preferably 2 ≦ a ≦ 4, particularly preferably a = 4. The obtained solid product is treated with an ester compound, and then treated with a mixture of an ether compound and titanium tetrachloride, or a mixture of an ether compound, titanium tetrachloride and an ester compound, to obtain a trivalent titanium compound. Containing solid catalyst,
(2) an organoaluminum compound,
(3) A catalyst system comprising an electron donating compound (dialkyldimethoxysilane or the like is preferably used) can be mentioned.
また、ホスファイト系(リン系)酸化防止剤として、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト(“Irgafos” 168、Mark 2112)、テトラキス(2,4-ジ-t-ブチルフェニル)-4-4’-ビフェニレン-ジホスホナイト(“Sandstab”P-EPQ)、ビス(2,4-ジ-t-ブチルフェニル)ペンタエリスリトールジホスファイト(“Ultranox”626,Mark PEP-24G)、ジステアリルペンタエリスリトールジホスファイト(Mark PEP-8)等が挙げられる。中でもこれらのヒンダードフェノール系とホスファイト系の両機能を合わせ持つ6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ[d,f][1,3,2]-ジオキサホスフェピン(“Sumilizer”GP)、及び、アクリル酸2[1-2-ヒドロキシ-3,5-ジ-t-ペンチルフェニル]エチル]-4,6-ジ-t-ペンチルフェニル(“Sumilizer”GS)が好ましい。特に、この両者の併用は、フィルム製膜に際し、特に20℃キシレン可溶部の分解抑制に効果を発揮し、耐低温衝撃性と耐ブロッキング性の両立に大きく寄与することから好ましい。かかるキシレン可溶部の分解が促進されると耐ブロッキング性が悪化する。 Specific examples of the antioxidant include hindered phenols such as 2,6-di-t-butylphenol (BHT), n-octadecyl-3- (3 ′, 5′-di-t-butyl-4 '-Hydroxyphenyl) propionate (“Irganox” 1076, “Sumilizer” BP-76), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (“Irganox”) "1010," Sumilizer "BP-101), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (" Irganox "3114, Mark AO-20), etc.
As phosphite (phosphorus) antioxidants, tris (2,4-di-t-butylphenyl) phosphite (“Irgafos” 168, Mark 2112), tetrakis (2,4-di-t-butyl) Phenyl) -4-4′-biphenylene-diphosphonite (“Sandstab” P-EPQ), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (“Ultranox” 626, Mark PEP-24G), And distearyl pentaerythritol diphosphite (Mark PEP-8). Among them, 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra- having both functions of these hindered phenols and phosphites t-Butyldibenz [d, f] [1,3,2] -dioxaphosphine (“Sumilizer” GP) and acrylic acid 2 [1-2-hydroxy-3,5-di-t-pentylphenyl ] Ethyl] -4,6-di-t-pentylphenyl ("Sumilizer" GS) is preferred. In particular, the combined use of both is preferable because it exerts an effect in suppressing the decomposition of the 20 ° C. xylene-soluble portion and greatly contributes to both low-temperature impact resistance and blocking resistance. When the decomposition of the xylene-soluble part is promoted, the blocking resistance is deteriorated.
ポリプロピレンペレット5gを沸騰キシレン(関東化学(株)1級)500mlに完全に溶解させた後に、20℃に降温し、4時間以上放置する。その後、これを析出物と溶液とに濾過して、可溶部と不溶部に分離した。可溶部は濾液を減圧下で固化した後、70℃で乾燥し、その重量を測定して含有量(重量%)を求めた。 (1) Content of 20 ° C. xylene soluble part 5 g of polypropylene pellets are completely dissolved in 500 ml of boiling xylene (Kanto Chemical Co., Ltd. Grade 1), then cooled to 20 ° C. and left for 4 hours or more. Thereafter, this was filtered into a precipitate and a solution, and separated into a soluble part and an insoluble part. The soluble part solidified the filtrate under reduced pressure, dried at 70 ° C., and measured its weight to determine the content (% by weight).
上記方法で分離したサンプルを用い、ウベローデ型粘度計を用いて、135℃テトラリン中で測定を行った。 (2) Intrinsic viscosity of 20 ° C. xylene insoluble part and soluble part Using the sample separated by the above method, measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer.
JIS K-7210-1999に準拠し、プロピレン・エチレンブロック共重合体は温度230℃、ポリエチレン系重合体は温度190℃で、それぞれ荷重21.18Nにて測定した。 (3) Melt flow rate (MFR)
In accordance with JIS K-7210-1999, the propylene / ethylene block copolymer was measured at a temperature of 230 ° C., and the polyethylene-based polymer was measured at a temperature of 190 ° C. under a load of 21.18 N, respectively.
JIS K-7112-1999に基づき、密度勾配管による測定方法で測定した。 (4) Density Based on JIS K-7112-1999, the density was measured by a measuring method using a density gradient tube.
厚さ12μmのPETフィルムと厚さ15μmのナイロン延伸フィルムと厚さ9μmのAL箔とコロナ放電処理を施した本発明のポリプロピレン系シーラントフィルム(ここで本発明フィルムと記載する。)とをウレタン系接着剤を用いて通常のドライラミネート法で貼合わせ、次の構成の積層体を作成した。
積層体構成:PETフィルム/接着剤/ON/接着剤/AL箔/接着剤/本発明フィルム
この積層体2枚を本発明フィルムが袋の内面になるようにして、富士インパルス社製CA-450-10型ヒートシーラーを使用し、加熱時間1.4秒(シール温度:約220℃)、冷却時間3.0秒で、製袋サイズ150mm×285mmのスタンディングパウチを作成した。この袋に濃度0.1%の食塩水1000cm3を充填した後、135℃で30分レトルト処理する。レトルト処理後の袋を0℃の冷蔵庫で保管した後、1袋ずつ55cmの高さから平らな床面に落下させ(n数20個)、破袋に至るまでの回数を記録する。本評価法ではn数20個で、破袋に至るまでの回数の平均が、35回以上であれば業務用の大型レトルト用途にも良好に使用できる。 (5) Low temperature impact resistance Polypropylene sealant film of the present invention subjected to corona discharge treatment with a PET film having a thickness of 12 μm, a stretched nylon film having a thickness of 15 μm, an AL foil having a thickness of 9 μm and a corona discharge treatment (herein referred to as the present invention film) Are laminated by a normal dry laminating method using a urethane-based adhesive to produce a laminate having the following configuration.
Laminate structure: PET film / adhesive / ON / adhesive / AL foil / adhesive / inventive film Two of these laminates were used as CA-450 manufactured by Fuji Impulse Co., Ltd. with the inventive film as the inner surface of the bag. Using a −10 type heat sealer, a standing pouch having a bag size of 150 mm × 285 mm was prepared with a heating time of 1.4 seconds (sealing temperature: about 220 ° C.) and a cooling time of 3.0 seconds. The bag is filled with 1000 cm 3 of 0.1% saline solution, and then retorted at 135 ° C. for 30 minutes. After storing the retort-treated bags in a refrigerator at 0 ° C., each bag is dropped from a height of 55 cm onto a flat floor (n number: 20), and the number of times until the bag is broken is recorded. In this evaluation method, the number of n is 20, and if the average number of times until the bag breaks is 35 times or more, it can be used well for large retort for business use.
(5)項と同じ積層体2枚を、本発明フィルムが袋の内面になるようにして、平板ヒートシーラーを使用し、シール温度180℃、シール圧力1kg/cm2、シール時間1秒の条件でヒートシールしたサンプルを、130℃×30分レトルト処理した後、オリエンテック社製テンシロンを使用して300mm/分の引張速度でヒートシール強度を測定した。本測定法でシール強度が60N/15mm 以上であれば、業務用の大型レトルト用途にも良好に使用できる。 (6) Heat seal strength Using two flat laminates as in (5), the film of the present invention becomes the inner surface of the bag, using a flat plate heat sealer, seal temperature 180 ° C., seal pressure 1 kg / cm 2 , A sample heat-sealed under the condition of a sealing time of 1 second was subjected to a retort treatment at 130 ° C. for 30 minutes, and then the heat seal strength was measured at a tensile speed of 300 mm / min using Tensilon manufactured by Orientec. If the seal strength is 60 N / 15 mm or more in this measurement method, it can be used well for commercial large retort applications.
(5)項と同じ積層体2枚を、本発明フィルムが袋の内面になるようにして、平板ヒートシーラーを使用し、シール温度180℃、シール圧力1kg/cm2、シール時間1秒の条件でヒートシールし、160mm×210mm(内部の寸法)の大きさの3方袋(平袋、シール幅5mm)を作成した。この袋に市販のレトルトカレー(ハウス食品工業社製のレトルトカレー「ククレカレー・辛口」)を充填した後、135℃で30分レトルト処理をした直後の積層体表面の凹凸発生状況を目視判定した。全く発生しないものをランク1、僅かに発生するものをランク2、軽度に発生するものをランク3、明確に発生するものをランク4、重度に発生するものをランク5として評価した。本評価法でランク1、2を耐ユズ肌発生性良好とした。 (7) Scratch-resistant skin resistance Two flat laminates as in (5) are used so that the film of the present invention becomes the inner surface of the bag, using a flat plate heat sealer, sealing temperature 180 ° C., sealing pressure 1 kg / cm 2. Heat sealing was performed under the condition of a sealing time of 1 second to prepare a three-sided bag (flat bag, seal width 5 mm) having a size of 160 mm × 210 mm (internal dimensions). After this bag was filled with a commercially available retort curry (a retort curry “Kukure Curry / Dry” manufactured by House Food Industry Co., Ltd.), the state of unevenness on the surface of the laminate immediately after retorting at 135 ° C. for 30 minutes was visually determined. The rating was evaluated as rank 1 for those that did not occur at all, rank 2 for those that occurred slightly, rank 3 for those that slightly occurred, rank 4 for those that occurred clearly, and rank 5 that occurred severely. In this evaluation method, ranks 1 and 2 were evaluated as good for the generation of scum skin.
幅30mmで長さ100mmのコロナ放電処理を施した本発明フィルムのサンプルを準備し、非コロナ処理面であるシール層どうしを30mm×40mmの範囲を重ね合わせて、500g/12cm2の荷重をかけ、80℃のオーブン内で24時間加熱処理した後、23℃、湿度65%の雰囲気下に30分以上放置した後、オリエンテック社製テンシロンを使用して300mm/分の引張速度で剪断剥離力を測定した。 本測定法で剪断剥離力が25N/12cm2以下であれば実用範囲とした。 (8) Blocking resistance A sample of the film of the present invention subjected to a corona discharge treatment having a width of 30 mm and a length of 100 mm was prepared, and a seal layer which is a non-corona treated surface was overlapped in a range of 30 mm × 40 mm to obtain 500 g / After applying a load of 12 cm 2 and heat-treating in an oven at 80 ° C. for 24 hours, leaving it in an atmosphere of 23 ° C. and 65% humidity for 30 minutes or more, using Tensilon manufactured by Orientec Co., Ltd., 300 mm / min. The shear peel force was measured at the tensile speed. In this measurement method, if the shear peeling force was 25 N / 12 cm 2 or less, it was regarded as a practical range.
サンプルを135℃で30分レトルト処理をした後、東洋精機製作所製MIT屈曲試験器を用いて、サンプル幅10mm、屈曲角度135度(左右)、荷重514gの条件で、100回屈曲した後、屈曲部の白化状況を目視判定した(n数5個)。全く白化しないものをランク1、僅かに白化するものをランク2、軽度に白化するものをランク3、明確に白化するものをランク4、白化して屈曲部が白くきつい線状となるものをランク5として評価した。本評価方法でランク1、2を耐屈曲白化性良好とした。 (9) Bending whitening resistance After retorting the sample at 135 ° C. for 30 minutes, using a MIT bending tester manufactured by Toyo Seiki Seisakusho, under the conditions of a sample width of 10 mm, a bending angle of 135 degrees (left and right), and a load of 514 g, After being bent 100 times, the whitening state of the bent portion was visually determined (n number of 5). Rank 1 for non-whitening, rank 2 for slightly whitening, rank 3 for light whitening, rank 4 for whitening clearly, rank whitening and the bent portion is white and linear Rated as 5. In this evaluation method, ranks 1 and 2 were considered to have good bending whitening resistance.
プロピレン・エチレンブロック共重合体(a)、低密度ポリエチレン系重合体(b)は次のものを使用した。 [Example 1]
The following were used for the propylene / ethylene block copolymer (a) and the low density polyethylene polymer (b).
20℃キシレン不溶部の含有量が80重量%、その極限粘度([η]H)が1.90dl/g、20℃キシレン可溶部の含有量が20重量%、その極限粘度([η]EP)が3.20dl/g、230℃でのMFRが2.3g/10分であり、酸化防止剤として“Sumilizer”GP300ppm及び“Sumilizer”GS750ppmを含有したプロピレン・エチレンブロック共重合体ペレットを使用した。 Propylene / ethylene block copolymer (a)
The content of the 20 ° C. xylene insoluble part is 80% by weight, its intrinsic viscosity ([η] H ) is 1.90 dl / g, the content of the 20 ° C. xylene soluble part is 20% by weight, its intrinsic viscosity ([η] EP ) is 3.20 dl / g, MFR at 230 ° C. is 2.3 g / 10 min, and propylene / ethylene block copolymer pellets containing “Sumilizer” GP 300 ppm and “Sumilizer” GS 750 ppm as antioxidants are used. did.
密度0.919g/cm3で、MFR2.0g/10分、共重合成分が1-ヘキセンである直鎖状低密度ポリエチレン(以下、L-LDPEと称すことがある。)((株)プライムポリマー製2022L)を使用した。 Low density polyethylene polymer (b)
Linear low density polyethylene (hereinafter sometimes referred to as L-LDPE) having a density of 0.919 g / cm 3 , MFR of 2.0 g / 10 min, and a copolymerization component of 1-hexene (hereinafter referred to as L-LDPE) (Prime Polymer Co., Ltd.) 2022L) was used.
実施例1で使用した(a)、(b)の混合比率を、(a)70重量%、(b)30重量%に変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 2]
A 70 μm thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) used in Example 1 was changed to (a) 70 wt% and (b) 30 wt%. It was. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
実施例1で使用した(a)、(b)の混合比率を、(a)85重量%、(b)15重量%に変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌性に若干劣るものの問題のないレベルであり、耐低温衝撃性、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 3]
A 70 μm-thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) used in Example 1 was changed to (a) 85 wt% and (b) 15 wt%. It was. The obtained film is slightly inferior to the skin-resistant skin, but at a level that does not cause any problems. It has excellent low-temperature impact resistance, sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
低密度ポリエチレン系重合体(b)として、密度が0.903g/cm3で、MFR3.8g/10分の共重合成分が1-ヘキセンである直鎖状低密度ポリエチレン((株)プライムポリマー製SP0540)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 4]
As the low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Prime Polymer Co., Ltd.) having a density of 0.903 g / cm 3 and a copolymerization component of MFR 3.8 g / 10 min of 1-hexene. SP0540) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
低密度ポリエチレン系重合体(b)として、密度が0.920g/cm3で、MFR7.0g/10分である低密度ポリエチレン(以下、LDPEと称すことがある。)(住友化学(株)製L705)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 5]
A low density polyethylene polymer (b) having a density of 0.920 g / cm 3 and a MFR of 7.0 g / 10 min (hereinafter sometimes referred to as LDPE) (manufactured by Sumitomo Chemical Co., Ltd.) L705) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
プロピレン・エチレンブロック共重合体を、20℃キシレン不溶部の割合を83%([η]H:1.92dl/g、[η]EP:3.25dl/g)としたものを準備し、実施例1と同様に厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 6]
A propylene / ethylene block copolymer having a 20% xylene insoluble part ratio of 83% ([η] H : 1.92 dl / g, [η] EP : 3.25 dl / g) was prepared and implemented. A 70 μm thick film was obtained in the same manner as in Example 1. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
プロピレン・エチレンブロック共重合体を、20℃キシレン不溶部の割合を77%([η]H:1.86dl/g、[η]EP:3.10dl/g)としたものを準備し、実施例1と同様に厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れ、業務用の大型のレトルト用途にも十分な性能を有するものであった。 [Example 7]
A propylene / ethylene block copolymer having a 20% xylene insoluble part ratio of 77% ([η] H : 1.86 dl / g, [η] EP : 3.10 dl / g) was prepared and carried out. A 70 μm thick film was obtained in the same manner as in Example 1. The resulting film is particularly excellent in low-temperature impact resistance and rust-proof skin resistance, as well as excellent sealing strength, blocking resistance, and bending whitening resistance, and is sufficient for commercial retort applications. It had a good performance.
プロピレン・エチレンブロック共重合体(a)を20℃キシレン不溶部の含有量が87重量%、その極限粘度([η]H)が1.93dl/g、20℃キシレン可溶部の含有量が13重量%、その極限粘度([η]EP)が3.15dl/g、230℃でのMFRが2.0g/10分であり、酸化防止剤として“イルガノックス”1010を700ppm、“イルガフォス”168を250ppm含有したプロピレン・エチレンブロック共重合体ペレットに変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性、耐ブロッキング性、ヒートシール性、耐屈曲白化性は良好なものの、耐低温衝撃性に劣るものであった。 [Comparative Example 1]
In the propylene / ethylene block copolymer (a), the content of the 20 ° C. xylene insoluble part is 87% by weight, its intrinsic viscosity ([η] H ) is 1.93 dl / g, and the content of the 20 ° C. xylene soluble part is 13 wt%, its intrinsic viscosity ([η] EP ) is 3.15 dl / g, MFR at 230 ° C. is 2.0 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Irgaphos” A film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the pellets were changed to propylene / ethylene block copolymer pellets containing 168 in 250 ppm. The resulting film had good resistance to low-temperature impacts, although it had good resistance to scratching skin, blocking resistance, heat sealability, and resistance to bending whitening.
プロピレン・エチレンブロック共重合体(a)を20℃キシレン不溶部の含有量が80重量%、その極限粘度([η]H)が1.90dl/g、20℃キシレン可溶部の含有量が20重量%、その極限粘度([η]EP)が2.80dl/g、230℃でのMFRが2.5g/10分であり、酸化防止剤として“イルガノックス”1010を700ppm、“Sumilizer”GP300ppm及び“Sumilizer”GS750ppmを含有したプロピレン・エチレンブロック共重合体ペレットに変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性、耐屈曲白化性は良好なものの、耐低温衝撃性、耐ブロッキング性、ヒートシール性に劣るものであった。 [Comparative Example 2]
In the propylene / ethylene block copolymer (a), the content of the 20 ° C. xylene insoluble part is 80% by weight, its intrinsic viscosity ([η] H ) is 1.90 dl / g, and the content of the 20 ° C. xylene soluble part is 20 wt%, its intrinsic viscosity ([η] EP ) is 2.80 dl / g, MFR at 230 ° C. is 2.5 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Sumilizer” A 70 μm-thick film was obtained in the same manner as in Example 1 except that the propylene / ethylene block copolymer pellets containing GP 300 ppm and “Sumilizer” GS 750 ppm were used. The obtained film was poor in low-temperature impact resistance, blocking resistance, and heat-sealability, although it had good resistance to scratching skin and bending whitening resistance.
プロピレン・エチレンブロック共重合体(a)を20℃キシレン不溶部の含有量が72重量%、その極限粘度([η]H)が1.89dl/g、20℃キシレン可溶部の含有量が28重量%、その極限粘度([η]EP)が3.21dl/g、230℃でのMFRが2.2g/10分であり、酸化防止剤として“イルガノックス”1010を700ppm、“Sumilizer”GP300ppm及び“Sumilizer”GS750ppmを含有したプロピレン・エチレンブロック共重合体ペレットに変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性、耐低温衝撃性、耐屈曲白化性は良好なものの、耐ブロッキング性、ヒートシール性に劣るものであった。 [Comparative Example 3]
In the propylene / ethylene block copolymer (a), the content of the 20 ° C. xylene insoluble part is 72% by weight, its intrinsic viscosity ([η] H ) is 1.89 dl / g, and the content of the 20 ° C. xylene soluble part is 28 wt%, its intrinsic viscosity ([η] EP ) is 3.21 dl / g, MFR at 230 ° C. is 2.2 g / 10 min, “Irganox” 1010 as an antioxidant, 700 ppm, “Sumilizer” A 70 μm-thick film was obtained in the same manner as in Example 1 except that the propylene / ethylene block copolymer pellets containing GP 300 ppm and “Sumilizer” GS 750 ppm were used. The obtained film had poor scratch resistance and heat-sealability, although it had good skin resistance, low-temperature impact resistance and bending whitening resistance.
プロピレン・エチレンブロック共重合体を、20℃キシレン不溶部の割合を81%([η]H:1.95dl/g、[η]EP:3.43dl/g)としたものを準備し、実施例1と同様に厚さ70μmフィルムを得た。得られたフィルムは、耐低温衝撃性、シール強度、耐ブロッキング性、耐屈曲白化性に優れたものであったが、耐ユズ肌発生性が不十分であった。 [Comparative Example 4]
A propylene / ethylene block copolymer having a 20 ° C. xylene insoluble part ratio of 81% ([η] H : 1.95 dl / g, [η] EP : 3.43 dl / g) was prepared and carried out. A 70 μm thick film was obtained in the same manner as in Example 1. The obtained film was excellent in low-temperature impact resistance, seal strength, blocking resistance, and bending whitening resistance, but was insufficient in the generation of crushed skin.
プロピレン・エチレンブロック共重合体を、20℃キシレン不溶部の割合を82%([η]H:1.65dl/g、[η]EP:3.11dl/g)としたものを準備し、実施例1と同様に厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性に優れたものであり、シール強度、耐ブロッキング性に優れたものであったが、耐低温衝撃性、耐屈曲白化性が不十分であった。 [Comparative Example 5]
A propylene / ethylene block copolymer having a 20% xylene insoluble portion ratio of 82% ([η] H : 1.65 dl / g, [η] EP : 3.11 dl / g) was prepared and carried out. A 70 μm thick film was obtained in the same manner as in Example 1. The obtained film was excellent in resistance to generation of scratches and was excellent in seal strength and blocking resistance, but was insufficient in low-temperature impact resistance and anti-bending whitening resistance.
実施例1の(a)、(b)の混合比率を、(a)65重量%、(b)35重量%に変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性、耐低温衝撃性、耐屈曲白化性は良好なものの、耐ブロッキング性、ヒートシール性に劣るものであった。 [Comparative Example 6]
A 70 μm thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) in Example 1 was changed to (a) 65 wt% and (b) 35 wt%. The obtained film had poor scratch resistance and heat-sealability, although it had good skin resistance, low-temperature impact resistance and bending whitening resistance.
実施例1の(a)、(b)の混合比率を、(a)90重量%、(b)10重量%に変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ブロッキング性、ヒートシール性は良好なものの、耐低温衝撃性や耐ユズ肌発生性、耐屈曲白化性に劣るものであった。 [Comparative Example 7]
A 70 μm thick film was obtained in the same manner as in Example 1 except that the mixing ratio of (a) and (b) in Example 1 was changed to (a) 90 wt% and (b) 10 wt%. Although the obtained film had good blocking resistance and heat sealability, it was inferior in resistance to low-temperature impact, resistance to crushed skin, and resistance to bending whitening.
低密度ポリエチレン系重合体(b)として、密度が0.960g/cm3で、MFR16.0g/10分の高密度ポリエチレン(以下、HDPEと称すことがある。)(京葉ポリエチレン(株)製KEIYOポリエチレンG1900)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐ユズ肌発生性は良好なものの、耐低温衝撃性、ヒートシール性に劣るものであった。 [Comparative Example 8]
The low density polyethylene polymer (b) has a density of 0.960 g / cm 3 and a MFR of 16.0 g / 10 min. High density polyethylene (hereinafter sometimes referred to as HDPE) (KEIYO manufactured by Keiyo Polyethylene Co., Ltd.) Polyethylene G1900) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. Although the obtained film had good crushed skin resistance, it was inferior in low-temperature impact resistance and heat sealability.
低密度ポリエチレン系重合体(b)として、密度が0.935g/cm3で、MFR3.0g/10分の共重合成分が1-ブテンである直鎖状低密度ポリエチレン(住友化学(株)製GA401)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、シール強度、耐ブロッキング性、耐屈曲白化性に優れていたものの、耐衝撃性が業務用の大型のレトルト用途には、不十分な性能であった。 [Comparative Example 9]
As the low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) having a density of 0.935 g / cm 3 and an MFR of 3.0 g / 10 min as a copolymer component of 1-butene. GA401) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The resulting film is particularly excellent in low-temperature impact resistance and scratch resistance, and has excellent sealing strength, blocking resistance, and bending whitening resistance. It was insufficient for large retort applications.
低密度ポリエチレン系重合体(b)として、密度が0.914g/cm3で、MFR11.0g/10分の共重合成分が1-ヘキセンである直鎖状低密度ポリエチレン((株)プライムポリマー製15100C)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、特に耐低温衝撃性、耐ユズ肌発生性に優れたものであり、また、耐ブロッキング性、耐屈曲白化性に優れていたものの、シール強度が低く、また、耐衝撃性が業務用の大型のレトルト用途には、不十分な性能であった。 [Comparative Example 10]
As a low density polyethylene polymer (b), a linear low density polyethylene (manufactured by Prime Polymer Co., Ltd.) having a density of 0.914 g / cm 3 and a copolymerization component of 11.0 g / 10 min of MFR of 1-hexene. 15100C) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The obtained film was particularly excellent in low temperature impact resistance and resistance to generation of crushed skin, and was excellent in blocking resistance and bending whitening resistance, but had low sealing strength and impact resistance. However, the performance was insufficient for large retort applications for business use.
低密度ポリエチレン系重合体(b)として、密度が0.875g/cm3で、MFR3.0g/10分である超低密度ポリエチレン(以下、VLDPEと称すことがある。)(ダウケミカル社製アフィニティKC8852G)を使用した。(b)を変更する以外は、実施例1と同様にして厚さ70μmフィルムを得た。得られたフィルムは、耐低温衝撃性や耐屈曲白化性に優れたものであったが、耐ユズ肌発生性、シール強度、耐ブロッキング性が不十分であった。 [Comparative Example 11]
As the low density polyethylene polymer (b), a very low density polyethylene (hereinafter sometimes referred to as VLDPE) having a density of 0.875 g / cm 3 and MFR of 3.0 g / 10 min (Affinity manufactured by Dow Chemical Co., Ltd.) KC8852G) was used. A 70 μm-thick film was obtained in the same manner as in Example 1 except that (b) was changed. The obtained film was excellent in low-temperature impact resistance and anti-bending whitening resistance, but was insufficient in the generation of crushed skin, seal strength, and blocking resistance.
Claims (3)
- プロピレン・エチレンブロック共重合体(a)70~85重量%、低密度ポリエチレン系重合体(b)15~30重量%を含む樹脂組成物からなるフィルムであって、プロピレン・エチレンブロック共重合体(a)は、20℃キシレン不溶部の割合が、(a)100重量%に対して75~85重量%で、該不溶部の極限粘度([η]H)が1.7~2.0dl/gであり、可溶部の極限粘度([η]EP)が3.0~3.4dl/gであり、低密度ポリエチレン系重合体(b)の密度が0.900~0.930g/cm3であり、メルトフローレートが1~10g/10分であるレトルト包装用ポリプロピレン系シーラントフィルム。 A film comprising a resin composition comprising 70 to 85% by weight of a propylene / ethylene block copolymer (a) and 15 to 30% by weight of a low density polyethylene polymer (b), wherein the propylene / ethylene block copolymer ( In a), the proportion of the 20 ° C. xylene insoluble part is 75 to 85% by weight with respect to (a) 100% by weight, and the intrinsic viscosity ([η] H ) of the insoluble part is 1.7 to 2.0 dl / g, the intrinsic viscosity ([η] EP ) of the soluble part is 3.0 to 3.4 dl / g, and the density of the low density polyethylene polymer (b) is 0.900 to 0.930 g / cm. 3. A polypropylene-based sealant film for retort packaging having a melt flow rate of 1 to 10 g / 10 min.
- 低密度ポリエチレン系重合体(b)が、直鎖状低密度ポリエチレンである請求項1に記載のレトルト包装用ポリプロピレン系シーラントフィルム。 The polypropylene sealant film for retort packaging according to claim 1, wherein the low density polyethylene polymer (b) is a linear low density polyethylene.
- 請求項1または2に記載のレトルト包装用ポリプロピレン系シーラントフィルムが、単層または2層以上のフィルムが積層された基材層の片面に積層された積層体。 The laminated body by which the polypropylene-type sealant film for retort packaging of Claim 1 or 2 was laminated | stacked on the single side | surface of the base material layer on which the film of the single layer or 2 layers or more was laminated | stacked.
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JP2016550280A JP6694613B2 (en) | 2015-08-31 | 2016-08-02 | Polypropylene sealant film for retort packaging and laminate using the same |
KR1020247012013A KR20240053004A (en) | 2015-08-31 | 2016-08-02 | Retort-packaging polypropylene-based sealant film and laminate using same |
KR1020177034359A KR20180046918A (en) | 2015-08-31 | 2016-08-02 | A polypropylene-based sealant film for use in retort packaging and a laminated body using the same |
US15/755,661 US20190193904A1 (en) | 2015-08-31 | 2016-08-02 | Polypropylene based sealant film for retort packaging, and laminate that uses the same |
CN201680041078.5A CN107848680B (en) | 2015-08-31 | 2016-08-02 | Boiling is packed for polypropylene-based sealing film and the laminated body using it |
PH12018500298A PH12018500298A1 (en) | 2015-08-31 | 2018-02-09 | Polypropylene based sealant film for retort packaging, and laminate that uses the same |
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JP (1) | JP6694613B2 (en) |
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JP6694613B2 (en) | 2020-05-20 |
TW201723066A (en) | 2017-07-01 |
KR20240053004A (en) | 2024-04-23 |
US20190193904A1 (en) | 2019-06-27 |
JPWO2017038349A1 (en) | 2018-06-14 |
KR20180046918A (en) | 2018-05-09 |
CN107848680B (en) | 2019-07-19 |
TWI771274B (en) | 2022-07-21 |
PH12018500298A1 (en) | 2018-08-13 |
CN107848680A (en) | 2018-03-27 |
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